JP7331635B2 - Optical filter and its use - Google Patents

Description

The present invention relates to optical filters and uses thereof. More specifically, the present invention relates to an optical filter that transmits near-infrared rays of at least part of the wavelengths and shields unnecessary wavelengths of light, and applications such as an optical sensor device using the optical filter.

In recent years, near-infrared rays have been used for mobile information terminal devices such as smartphones, tablet terminals, and wearable devices, as well as for advanced driver assistance systems, automatic driving systems, aircraft, unmanned aerial vehicles, robots, agricultural machinery, and medical equipment. Development of various optical sensor devices using .

In information terminal devices, optical sensor devices are being considered for various applications. Healthcare applications such as medium oxygen concentration measurement can be mentioned.

In an optical sensor device using near-infrared rays, it is important to cut unnecessary wavelengths of light in order for the sensing function to work accurately. Also, depending on the wavelength of the near-infrared rays used for sensing, near-infrared rays with shorter wavelengths are cut (for example, when near-infrared rays around 940 nm are used for sensing, near-infrared rays up to around 900 nm are cut in addition to visible rays. By doing so, the noise during sensing can be reduced, and the characteristics of the optical sensor device can be improved.

On the other hand, various optical sensor parts such as mobile information terminal devices are becoming thinner and wider, and the ratio of incident light from oblique directions increases more than ever before. In order to improve the sensor accuracy, it is required that the spectral characteristics of the light reaching the optical sensor (cutting characteristics of visible light and near-infrared rays of unnecessary wavelengths) do not change even when the incident light comes from an oblique direction. .

For example, as a means for cutting visible light and transmitting near-infrared rays of a specific wavelength, a bandpass filter has been disclosed in which multilayer thin films of high refractive index materials and low refractive index materials are alternately laminated on a glass substrate (for example, patent Reference 1). However, an optical filter formed with such a multilayer thin film has optical characteristics that vary greatly depending on the incident angle of incident light. Therefore, there is a problem that the detection accuracy of the optical sensor that performs wide-angle sensing is lowered.

As an optical filter that transmits near-infrared rays of a specific wavelength, as an optical filter with little incident angle dependence, a multilayer film using amorphous silicon (see, for example, Patent Document 2) and a high refractive index layer in a dielectric multilayer film are used. There are known optical filters designed by such design (see, for example, Patent Documents 3 and 4), and optical filters combined with a compound that absorbs near-infrared rays of a specific wavelength (eg, Patent Document 5). The change in optical characteristics due to the incident angle in the near-infrared ray transmission band is smaller than that of conventional dielectric multilayer films, and the incident angle dependency of the detection sensitivity in the light source wavelength region of the optical sensor is reduced.

Mobile information terminals, which have been rapidly becoming smaller and lighter in recent years, self-driving system applications, aircraft applications, unmanned aircraft applications, and robot applications are often used outdoors and are often exposed to noise due to sunlight. . Sunlight noise is offset (removed) according to the amount of light received by the ambient light sensor installed adjacent to the optical sensor, but conventional optical filters that transmit near-infrared rays of specific wavelengths are incident angle dependent. The improvement in properties is not sufficient, and the amount of offset of sunlight varies depending on the incident angle, and there are cases where it cannot be suitably used in mobile information terminal applications, automatic driving system applications, aircraft applications, unmanned aerial vehicles, and robot applications. In addition, when used outdoors, the temperature often rises due to solar radiation, etc., and conventional optical filters that transmit near-infrared rays of specific wavelengths suffer from changes in optical characteristics due to temperature rise. In some cases, it could not be suitably used for operation system applications, aircraft applications, unmanned aircraft applications, and robot applications.

JP 2015-184627 A U.S. Patent Application Publication No. 2017/0336544 JP 2015-111241 A International Publication No. 2013/015303 International Publication No. 2017/213047

In the present invention, the amount of noise caused by sunlight is less dependent on the angle of incidence even when the angle of incidence is increased due to the reduction in the height and widening of the angle of the equipment in which the optical sensor device is installed, and the transmission wavelength changes even when the temperature changes. It is an object of the present invention to provide an optical filter which has a small amount of light and is capable of both transmitting near-infrared rays of a specific wavelength and shielding other near-infrared rays.

The inventor of the present invention has made intensive studies to solve the above problems. As a result, the inventors have found that the above problems can be solved by an optical filter having specific optical properties, and completed the present invention. Examples of aspects of the invention are provided below.

[1] An optical filter having a substrate and a dielectric multilayer film formed on at least one surface of the substrate and transmitting at least part of near-infrared rays,
An optical filter that satisfies the following requirements (A) and (B) at a wavelength of 300 to 1200 nm:
(A) The maximum transmittance T ^θ _MAX (%) in the wavelength range of 900 to 1060 nm is is 50% or more;
(B) λ ^θ _MAX (nm) is the wavelength at which T ^θ _MAX (%) is obtained in light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. and λ ^θ B ₅₀ (nm) is the shortest wavelength at which the transmittance is 50% in the region longer than λ θ _MAX (nm), | ^{λ 0 B} ₅₀ -λ ³⁰ B ₅₀ | is.
[2] The optical filter according to [1], which further satisfies the following requirement (C):
(C) Average transmittance T in the range of 750 to (λ ^θ _MAX -50) nm for light rays incident at an angle of θ degrees (θ is 0 and 30) from the direction perpendicular to the surface of the optical filter The sum of ^θ _AVG(1) (%) and average transmittance T ^θ _AVG(2) (%) in the range from (λ ^θ _MAX +50) to 1110 nm is 20% or less.
[3] The optical filter according to item [1] or [2] that further satisfies the following requirement (D):
(D) Transmittance of 50 in a wavelength region shorter than λ ^θ _MAX (nm) for light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. % is λ ^θ A ₅₀ (nm), |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |≦10.
[4] The optical filter according to [3], which further satisfies the following requirement (E):
(E) |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |+|λ ⁰ B ₅₀ −λ ³⁰ B ₅₀ |≦15.
[5] The optical filter according to any one of items [1] to [4], which further satisfies the following requirement (F):
(F) Average transmittance T ^θ _AVG(3) ( %) is 10% or less.
[6] The optical filter according to any one of items [1] to [5], wherein the T ^θ _MAX (%) is 70% or more.
[7] The optical filter according to any one of items [1] to [6], wherein all layers constituting the dielectric multilayer film have a refractive index of less than 3.5.
[8] The optical filter according to any one of items [1] to [7], wherein the dielectric multilayer film is composed of a layer made of TiO ₂ and a layer made of SiO ₂ .
[9] The optical filter of item [8], wherein all the layers made of _SiO2 constituting the dielectric multilayer film have a refractive index of 1.47 or more.
[10] The optical filter of any one of items [1] to [9], wherein the dielectric multilayer film includes at least one layer having a physical thickness of 300 nm or more and 800 nm or less.
[11] An item characterized in that at least one of the dielectric multilayer films has one minimum value of transmittance between an incident angle of 0 degree and 30 degrees at a wavelength of (λ ^θ B ₅₀ -5) nm. The optical filter according to any one of [1] to [10].
[12] The optical filter according to any one of items [1] to [11], which is for an optical sensor device.
[13] An optical sensor device comprising the optical filter according to any one of items [1] to [12].
[14] A biometric authentication device comprising the optical filter according to any one of items [1] to [12].
[15] A solid-state imaging device comprising the optical filter according to any one of items [1] to [12].
[16] A camera module comprising the optical filter according to any one of items [1] to [12].

The optical filter of the present invention has partial near-infrared transmittance properties, undergoes little change in optical properties even when light is incident from an oblique direction, and undergoes little change in transmission wavelength even when the temperature changes, making it suitable for use in optical sensors. used for

FIG. 1 is a schematic cross-sectional view showing a structural example of the optical filter of the present invention. FIG. 2A is a schematic diagram showing a method of measuring the transmittance of light incident on the surface of the optical filter in the direction perpendicular to it. FIG. 2B is a schematic diagram showing a method of measuring the transmittance of light incident on the surface of the optical filter at an angle of 30 degrees from the vertical direction. FIG. 3 is a schematic cross-sectional view showing an example of a solid-state imaging device, a camera module, and a sensor including the optical filter of the present invention. FIG. 4 is a diagram showing an example of wavelength-dependent sensitivity of a near-infrared sensor pixel. FIG. 5 shows irradiation dose data in Gifu on a certain date and time, which is published by the New Energy and Industrial Technology Development Organization, a national research and development agency. 6A is a spectral transmission spectrum of the optical filter obtained in Example 1. FIG. FIG. 6B is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 1. FIG. FIG. 7 is a diagram showing the incident angle dependence of transmittance at a wavelength of 968 nm when the dielectric multilayer film of design (I) in Example 1 is provided on a glass substrate. 8(a) is a spectral transmission spectrum of the optical filter obtained in Example 2. FIG. FIG. 8B is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 2. FIG. 9(a) is the spectral transmission spectrum of the optical filter obtained in Example 3. FIG. FIG. 9B is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 3. FIG. 10(a) is a spectral transmission spectrum of the optical filter obtained in Example 4. FIG. FIG. 10(b) is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 4. FIG. 11(a) is a spectral transmission spectrum of the optical filter obtained in Example 5. FIG. FIG. 11(b) is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 5. FIG. 12(a) is the spectral transmission spectrum of the optical filter obtained in Example 6. FIG. FIG. 12(b) is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Example 6. FIG. 13(a) is a spectral transmission spectrum of the optical filter obtained in Comparative Example 1. FIG. 13(b) is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Comparative Example 1. FIG. FIG. 14 is a diagram showing incident angle dependence of transmittance at a wavelength of 1000 nm when the dielectric multilayer film of design (VIII) in Comparative Example 1 is provided on a glass substrate. 15(a) is a spectral transmission spectrum of the optical filter obtained in Comparative Example 2. FIG. FIG. 15(b) is a diagram showing sensitivity data for each wavelength of the near-infrared sensor under sunlight in Comparative Example 2. FIG. 16(a) is the spectral transmission spectrum of the optical filter obtained in Comparative Example 3. FIG. FIG. 16(b) is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Comparative Example 3. FIG. 17(a) is a spectral transmission spectrum of the optical filter obtained in Comparative Example 4. FIG. FIG. 17B is a diagram showing sensitivity data by wavelength of the near-infrared sensor under sunlight in Comparative Example 4. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of an optical filter according to the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different aspects and should not be construed as being limited to the description of the embodiments exemplified below. In order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example and limits the interpretation of the present invention. not a thing In addition, in this specification and each figure, the same reference numerals or similar reference numerals (numbers followed by "'" etc.) are attached to the same elements as those described above with respect to the previous figures. and detailed description may be omitted as appropriate.

In this specification, the term "upper" refers to a relative position with respect to the main surface of the supporting substrate (for example, the surface on which the solid-state imaging device is arranged), and the direction away from the main surface of the supporting substrate is " Above. In this drawing, "top" is the upper side toward the paper surface. "Above" includes the case of being in contact with the object (that is, the case of "on") and the case of being located above the object (that is, the case of "over"). Conversely, "lower" refers to a relative position with respect to the major surface of the supporting substrate, and the direction toward the major surface of the supporting substrate is "lower". In this drawing, the downward direction toward the paper surface is "bottom".

Further, in this specification, "maximum transmittance at wavelength (V) ~ (W) nm" is synonymous with "maximum transmittance at wavelength (V) ~ (W) nm", and "wavelength (V) "Average transmittance at ~ (W) nm" is synonymous with "average value of transmittance over the entire wavelength range at wavelengths (V) ~ (W) nm". In this case, V and W are set to different numerical values.

[Optical filter]
An optical filter of the present invention has a substrate and a dielectric multilayer film formed on at least one surface of the substrate, and transmits at least part of near-infrared rays, and has a wavelength of 300. It is characterized by satisfying the following requirements (A) and (B) at ~1200 nm.
(A) The maximum transmittance T ^θ _MAX (%) in the wavelength range of 900 to 1060 nm is 50% or more.
(B) λ ^θ _MAX (nm) is the wavelength at which T ^θ _MAX (%) is obtained in light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. and λ ^θ B ₅₀ (nm) is the shortest wavelength at which the transmittance is 50% in the region longer than λ θ _MAX (nm), | ^{λ 0 B} ₅₀ -λ ³⁰ B ₅₀ | is.

An optical filter that satisfies the requirement (A) has a light transmission band in at least part of the wavelength range of 900 to 1060 nm. As described above, the optical filter of the present invention has near-infrared transmission characteristics in a specific wavelength region, so that near-infrared rays necessary for sensing can be efficiently taken in, and good sensing performance can be achieved. The T ^θ _MAX (%) is preferably 60% or more, more preferably 70% or more. The phrase "T ^θ _MAX (%) is 50% or more" means that T ^θ _MAX (%) is 50% or more regardless of whether the θ degree is 0 degree or 30 degrees. The same applies to other expressions using θ.

The light transmission band is a continuous wavelength band in which the transmittance of the optical filter measured under the above conditions is 45% or more, and the width is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 30 nm or more.

By using an optical filter that satisfies the requirement (B), it is possible to improve the incident angle dependency on the longer wavelength side than the light transmission band. The absolute value |λ ⁰ B ₅₀ −λ ³⁰ B ₅₀ | is preferably 9.5 nm or less, more preferably 9.0 nm or less, still more preferably 0.1 to 8.5 nm. The λ ^θ _MAX (nm) is preferably 850 to 1040 nm, more preferably 900 to 1000 nm, from the viewpoint of improving sensing sensitivity.

Preferably, the optical filter of the present invention further satisfies the following requirement (C).
(C) Average transmittance T in the range of 750 to (λ ^θ _MAX -50) nm for light rays incident at an angle of θ degrees (θ is 0 and 30) from the direction perpendicular to the surface of the optical filter The sum of ^θ _AVG(1) (%) and average transmittance T ^θ _AVG(2) (%) in the range from (λ ^θ _MAX +50) to 1110 nm is 20% or less.

An optical filter that satisfies the requirement (C) has near-infrared shielding regions on the long-wavelength side and short-wavelength side of the light transmission band. is possible. The sum of T ^θ _AVG(1) (%) and T ^θ _AVG(2) (%) in requirement (C) is preferably 15% or less, more preferably 10% or less.

Preferably, the optical filter of the present invention further satisfies the following requirement (D).
(D) Transmittance of 50 in a wavelength region shorter than λ ^θ _MAX (nm) for light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. % is λ ^θ A ₅₀ (nm), |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |≦10.

By using an optical filter that satisfies the requirement (D), it is possible to improve the incident angle dependency on the short wavelength side of the light transmission band. The absolute value |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ | is preferably 8 nm or less, more preferably 6 nm or less, still more preferably 0.1 to 4 nm.

Preferably, the optical filter of the present invention further satisfies the following requirement (E).
(E) |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |+|λ ⁰ B ₅₀ −λ ³⁰ B ₅₀ |≦15.
By using an optical filter that satisfies the requirement (E), it is possible to improve the incident angle dependency on the long wavelength side and the short wavelength side of the light transmission band. The sum of the absolute value |λ ⁰ B ₅₀ −λ ³⁰ B ₅₀ | and the absolute value |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ | 2 to 10 nm.

Preferably, the optical filter of the present invention further satisfies the following requirement (F).
(F) Average transmittance T ^θ _AVG(3) ( %) is 10% or less.

By using an optical filter that satisfies the requirement (F), visible light that is unnecessary for near-infrared sensing can be efficiently cut, and excellent sensing performance with little noise can be achieved. The T ^θ _AVG(3) (%) is preferably 8% or less, more preferably 5% or less, and particularly preferably 2% or less.

[Base material]
The base material constituting the optical filter of the present invention is not particularly limited in material, shape, etc., as long as it does not impair the effects of the present invention, but it is preferably a plate-like body having transparency. Examples of materials for such substrates include glass plates, tempered glass plates, special glasses such as phosphate glass, fluorophosphate glass, alumina glass, yttrium aluminate, and yttrium oxide, and transparent resins.

FIG. 1 shows a configuration example of an optical filter. The substrate may be a single layer (see, for example, FIGS. 1(A) to (D), (F) and (G)) or a multilayer (see, for example, FIG. 1(E)), and is selected from the above materials. or a plurality of materials, or a material that is appropriately mixed. The substrate preferably includes a transparent resin layer containing a compound (Z) having an absorption maximum in the wavelength range of 700 to 930 nm.

<Glass plate>
Examples of the glass plate include silicate glass, soda lime glass, borosilicate glass, and quartz glass.

<Tempered glass plate>
Examples of the tempered glass plate include physically tempered glass, tempered laminated glass, and chemically tempered glass. Among these, chemically strengthened glass is preferable because it has a thin compressed layer and can be processed to have a thin base material. Specific examples of the chemically strengthened glass include "Dragontrail" manufactured by Asahi Glass Co., Ltd. and "Gorilla Glass" manufactured by Corning.

<Special glass>
Examples of the phosphate glass and the fluorophosphate glass include phosphate glass described in JP-A-2013-119517 and fluorophosphate glass described in JP-A-2011-116654. Examples of the alumina glass include "Hiceram" manufactured by NGK Insulators, Ltd., and the like. Examples of the yttrium aluminate and the yttrium oxide include "EXYRIA (registered trademark)" manufactured by CoorsTek.

<Transparent resin>
The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. Resins having a glass transition temperature (Tg) of preferably 110 to 380.degree. C., more preferably 110 to 370.degree. C., and even more preferably 120 to 360.degree. Moreover, it is particularly preferable that the glass transition temperature of the resin is 140° C. or higher, since a film in which a dielectric multilayer film can be vapor-deposited at a higher temperature can be obtained.

As the transparent resin, when a resin plate having a thickness of 0.1 mm is formed from the resin, the light transmittance of the resin plate in the wavelength range of 800 to 1060 nm is preferably 75 to 95%, more preferably 78%. Resins of up to 95%, particularly preferably 80-95%, can be used. If a resin having a total light transmittance in such a range is used, the obtained substrate exhibits good transparency as an optical film.

The polystyrene equivalent weight average molecular weight (Mw) of the transparent resin measured by gel permeation chromatography (GPC) is usually 15,000 to 350,000, preferably 30,000 to 250,000. The average molecular weight (Mn) is usually 10,000-150,000, preferably 20,000-100,000.

Examples of transparent resins include cyclic (poly)olefin-based resins, aromatic polyether-based resins, polyimide-based resins, fluorene polycarbonate-based resins, fluorene polyester-based resins, polycarbonate-based resins, polyamide (aramid)-based resins, and polyarylate-based resins. Resins, polysulfone-based resins, polyethersulfone-based resins, polyparaphenylene-based resins, polyamideimide-based resins, polyethylene naphthalate (PEN)-based resins, fluorinated aromatic polymer-based resins, (modified) acrylic-based resins, epoxy-based resins Resins, allyl ester curable resins, silsesquioxane ultraviolet curable resins, acrylic ultraviolet curable resins, and vinyl ultraviolet curable resins can be mentioned.

≪Cyclic (poly)olefin resin≫
As the cyclic (poly)olefin resin, at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) and resins obtained by hydrogenating said resins are preferred.

式（Ｘ₀）中、Ｒ^x1～Ｒ^x4はそれぞれ独立に、下記（i'）～（ix'）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xはそれぞれ独立に、０～４の整数を表す。
（i'）水素原子
（ii'）ハロゲン原子
（iii'）トリアルキルシリル基
（iv'）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１～３０の炭化水素基
（v'）置換または非置換の炭素数１～３０の炭化水素基
（vi'）極性基（但し、（ii'）および（iv'）を除く。）
（vii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1～Ｒ^x4は、それぞれ独立に前記（ｉ'）～（vi'）より選ばれる原子または基を表す。）
（viii'）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1～Ｒ^x4は、それぞれ独立に前記（i'）～（vi'）より選ばれる原子または基を表す。）
（ix'）Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4は、それぞれ独立に前記（i'）～（vi'）より選ばれる原子または基を表す。）

In formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or group selected from (i') to (ix') below, k ^x , m ^x and p ^x each independently represent 0 Represents an integer from ~4.
(i') a hydrogen atom (ii') a halogen atom (iii') a trialkylsilyl group (iv') a substituted or unsubstituted carbon number of 1 having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom ~30 hydrocarbon group (v') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (ii') and (iv'))
(vii') an alkylidene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 together (provided that R ^x1 to R ^x4 not involved in the bonding are each independently ) to represent an atom or group selected from (vi').)
(viii') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R ^x1 to R ^x4 each independently represents an atom or group selected from the above (i') to (vi').)
(ix') A monocyclic hydrocarbon ring or heterocyclic ring formed by bonding R ^x2 and R ^x3 together (provided that R ^x1 and R ^x4 not involved in the bonding are each independently ') to represent an atom or group selected from (vi').)

式（Ｙ₀）中、Ｒ^y1およびＲ^y2はそれぞれ独立に、前記（i'）～（vi'）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yはそれぞれ独立に、０～４の整数を表す。

In formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i′) to (vi′), or R ^y1 and R ^y2 are mutually bonded to Each of k ^y and p ^y independently represents an integer from 0 to 4, representing a formed monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring.

≪Aromatic polyether resin≫
The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of structural units represented by the following formula (1) and structural units represented by the following formula (2).

式（１）中、Ｒ¹～Ｒ⁴はそれぞれ独立に、炭素数１～１２の１価の有機基を示し、ａ～ｄはそれぞれ独立に、０～４の整数を示す。

In formula (1), R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4.

式（２）中、Ｒ¹～Ｒ⁴およびａ～ｄはそれぞれ独立に、前記式（１）中のＲ¹～Ｒ⁴およびａ～ｄと同義であり、Ｙは、単結合、－ＳＯ₂－または－ＣＯ－を示し、Ｒ⁷およびＲ⁸はそれぞれ独立に、ハロゲン原子、炭素数１～１２の１価の有機基またはニトロ基を示し、ｇおよびｈはそれぞれ独立に、０～４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁷はシアノ基ではない。

In formula (2), R ¹ to R ⁴ and a to d are each independently defined as R ¹ to R ⁴ and a to d in formula (1) above; Y is a single bond _; - or -CO-, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent 0 to 4 It represents an integer, and m represents 0 or 1. However, when m is 0, ^R7 is not a cyano group.

In addition, the aromatic polyether-based resin further has at least one structural unit selected from the group consisting of structural units represented by the following formula (3) and structural units represented by the following formula (4). is preferred.

式（３）中、Ｒ⁵およびＲ⁶はそれぞれ独立に、炭素数１～１２の１価の有機基を示し、Ｚは、単結合、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－または炭素数１～１２の２価の有機基を示し、ｅおよびｆはそれぞれ独立に、０～４の整数を示し、ｎは０または１を示す。

In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, —O—, —S—, —SO ₂ —, — represents CO—, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represents an integer of 0 to 4, and n represents 0 or 1;

式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈはそれぞれ独立に、前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆはそれぞれ独立に、前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。

In formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in formula (2); ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the above formula (3).

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in a repeating unit. Can be synthesized.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety.

≪Fluorene polyester resin≫
The fluorene polyester-based resin is not particularly limited, and may be a polyester resin containing a fluorene moiety. can be done.

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is preferably a polymer containing a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.

<<Acrylic UV curable resin>>
The acrylic UV-curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. can be listed. The acrylic UV-curable resin is a substrate obtained by laminating a transparent resin layer containing the compound (Z) and a curable resin on a glass support or a base resin support as the substrate (i), or When using a substrate in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing the compound (Z), it can be particularly preferably used as the curable resin. .

≪Commercial product≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic (poly)olefin resins include Arton manufactured by JSR Corporation, Zeonor manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. . Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. and the like can be mentioned as commercial products of polyether sulfone-based resins. Commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Commercial products of polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc., and the like. OKP4HT manufactured by Osaka Gas Chemicals Co., Ltd. and the like can be cited as commercial products of fluorene polyester-based resins. Examples of commercially available acrylic resins include Acryvure manufactured by Nippon Shokubai Co., Ltd., and the like. Commercially available silsesquioxane-based UV-curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd., and the like.

<Compound (Z)>
The compound (Z) is not particularly limited as long as it has an absorption maximum in the wavelength range of 700 to 930 nm, but it is preferably a solvent-soluble dye compound. Examples of the compound (Z) include squarylium-based compounds, croconium-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, polymethine-based compounds, cyanine-based compounds, tetraazaporphyrin-based compounds, porphyrin-based compounds, triarylmethane-based compounds, Subphthalocyanine compounds, perylene compounds, semisquarylium compounds, styryl compounds, phenazine compounds, pyridomethene-boron complex compounds, pyrazine-boron complex compounds, pyridone azo compounds, xanthene compounds, and dipyrromethene compounds. . Among these are squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, naphthalocyanine-based compounds, pyrrolopyrrole-based compounds, croconium-based compounds, hexaphylline-based compounds, metal dithiolate-based compounds, and ring-expanded BODIPY (boron dipyrromethene). A squarylium-based compound, a cyanine-based compound, a croconium-based compound, and a pyrrolopyrrole-based compound are more preferable, and a squarylium-based compound represented by the following formula (Z) is particularly preferable. By using such a compound (Z), it is possible to simultaneously achieve an efficient light-cutting property in the vicinity of the maximum absorption wavelength and a steep spectral shape. Compound (Z) may be used alone or in combination of two or more.

式（Ｚ）中、置換ユニットＡおよびＢは、それぞれ独立に下記式（Ｉ）および（ＩＩ）で表される置換ユニットのいずれかを表す。

In formula (Z), substituted units A and B each independently represent any of the substituted units represented by formulas (I) and (II) below.

式（Ｉ）および（ＩＩ）中、波線で表した部分が中央四員環との結合部位を表し、 Ｘは、独立に酸素原子、硫黄原子、セレン原子、テルル原子または－ＮＲ⁸－を表し、 Ｒ¹～Ｒ⁸は、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、－ＮＲ^gＲ^h基、－ＳＲⁱ基、－ＳＯ₂Ｒⁱ基、－ＯＳＯ₂Ｒⁱ基または下記Ｌ^a～Ｌ^hのいずれかを表し、Ｒ^gおよびＲ^hは、それぞれ独立に水素原子、－Ｃ（Ｏ）Ｒⁱ基または下記Ｌ^a～Ｌ^eのいずれかを表し、Ｒⁱは下記Ｌ^a～Ｌ^eのいずれかを表し、
（Ｌ^a）炭素数１～１２の脂肪族炭化水素基
（Ｌ^b）炭素数１～１２のハロゲン置換アルキル基
（Ｌ^c）炭素数３～１４の脂環式炭化水素基
（Ｌ^d）炭素数６～１４の芳香族炭化水素基
（Ｌ^e）炭素数３～１４の複素環基
（Ｌ^f）炭素数１～１２のアルコキシ基
（Ｌ^g）置換基Ｌを有してもよい炭素数１～１２のアシル基、
（Ｌ^h）置換基Ｌを有してもよい炭素数１～１２のアルコキシカルボニル基

In formulas (I) and (II), the part represented by the wavy line represents the bonding site with the central four-membered ring, and X independently represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or -NR ⁸ -. , R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -NR ^g R ^h group, a -SR ⁱ group and a -SO ₂ R ⁱ group, —OSO ₂ R ⁱ group, or any one of L ^a to L ^h below, wherein R ^g and R ^h are each independently a hydrogen atom, —C(O)R ⁱ group, or L ^a to L Represents any one of ^e , R ⁱ represents any one of L ^a to L ^e below,
(L ^a ) Aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) Halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ) Alicyclic hydrocarbon group having 3 to 14 carbon atoms (L ^d ) Carbon Aromatic hydrocarbon group having 6 to 14 carbon atoms (L ^e ) Heterocyclic group having 3 to 14 carbon atoms (L ^f ) Alkoxy group having 1 to 12 carbon atoms (L ^g ) Number of carbon atoms which may have substituent L 1 to 12 acyl groups,
(L ^h ) an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent L

The substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. It is at least one selected from the group consisting of a hydrogen group and a heterocyclic group having 3 to 14 carbon atoms.

R ¹ is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group and nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group and hydroxyl group.

R ² to R ⁷ are preferably each independently hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-blue group and tert- Butyl group, cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methyl acetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group, n- butylthio group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, hydroxyl group, dimethylamino group, methoxy group, ethoxy group, acetylamino group, propionylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, methylthio group and ethylthio group.

R ⁸ is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n- hexyl group, n-heptyl group, n-octyl group, n-octyl group, n-nonyl group, n-decyl group, phenyl group, more preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group and n-decyl group.

X is preferably an oxygen atom, a sulfur atom or -NR ⁸ -, particularly preferably an oxygen atom or a sulfur atom in the substitution unit of formula (I), and - in the substitution unit of formula (II) NR ⁸ -.

The structure of the squarylium-based compound can be represented not only by a description method such as the following formula (Z1), but also by a description method that takes a resonance structure such as the following formula (Z2). That is, the difference between formula (Z1) below and formula (Z2) below is only the method of describing the structure, and both represent the same compound. In the present invention, unless otherwise specified, the structure of the squarylium-based compound is represented by a method of description such as the following formula (Z1).

さらに、例えば、下記式（Ｚ１）で表される化合物と下記式（Ｚ３）で表される化合物は、同一の化合物であると見なすことができる。

Furthermore, for example, the compound represented by the following formula (Z1) and the compound represented by the following formula (Z3) can be regarded as the same compound.

式（Ｚ）で表される化合物において、中央の四員環に結合している左右のユニットは それぞれ式（Ｉ）または式（ＩＩ）で表されるものであれば同一であっても異なっていてもよいが、ユニット中の置換基も含めて同一であった方が合成上容易であるため好ましい。つまり、式（Ｚ）で表される化合物のうち、下記式（ＩＩＩ）または式（ＩＶ）で表されるものが好ましい。

In the compound represented by formula (Z), the left and right units bonded to the central four-membered ring may be the same or different as long as they are represented by formula (I) or formula (II). However, it is preferable for the units to be the same, including the substituents, for ease of synthesis. That is, among the compounds represented by formula (Z), those represented by formula (III) or formula (IV) below are preferred.

式（Ｚ）で表される化合物の具体例としては、例えば、下記表１および表２に記載の化合物（ｚ－１）～（ｚ－５８）、ならびに、下記化学式で表わされる化合物（ｚ－５９）および化合物（ｚ－６０）を挙げることができる。

Specific examples of the compound represented by formula (Z) include compounds (z-1) to (z-58) shown in Tables 1 and 2 below, and compounds (z- 59) and compound (z-60).

上記式（Ｚ）で表されるスクアリリウム系化合物以外のスクアリリウム系化合物、シアニン系化合物、ピロロピロール系化合物としては、波長７００～９００ｎｍに吸収極大を有すれば特に限定されないが、例えば、下記のような化合物類（ｚ－６１）～（ｚ－６４）を挙げることができる。

The squarylium-based compound, cyanine-based compound, and pyrrolopyrrole-based compound other than the squarylium-based compound represented by the above formula (Z) are not particularly limited as long as they have an absorption maximum at a wavelength of 700 to 900 nm. compounds (z-61) to (z-64).

化合物（Ｚ）の吸収極大波長は７００～９３０ｎｍであり、好ましくは７２０～９２０ｎｍ以下、さらに好ましくは７３０ｎｍ以上９００ｎｍ以下、特に好ましくは７５０ｎｍ以上８９０ｎｍ以下 である。化合物（Ｚ）の吸収極大波長がこのような範囲にあると、近赤外センシングに有用な波長の光を透過させつつ不要な近赤外線をカットすることができ、近赤外透過帯の入射角依存性を低減させることができる。

The maximum absorption wavelength of compound (Z) is from 700 to 930 nm, preferably from 720 to 920 nm, more preferably from 730 nm to 900 nm, particularly preferably from 750 nm to 890 nm. When the absorption maximum wavelength of the compound (Z) is in such a range, unnecessary near infrared rays can be cut while transmitting light of a wavelength useful for near infrared sensing, and the incident angle of the near infrared transmission band Dependencies can be reduced.

The compound (Z) may be synthesized by a generally known method. can be synthesized by referring to the method described in .

The content of the compound (Z) is, for example, a substrate made of a transparent resin substrate containing the compound (Z), or an overcoat layer made of a curable resin or the like on a transparent resin substrate. When using a substrate having a laminated resin layer, it is preferably 0.01 to 2.0 parts by mass, more preferably 0.02 to 1.5 parts by mass, particularly preferably 100 parts by mass of the transparent resin. is 0.03 to 1.0 parts by mass, and a transparent overcoat layer such as an overcoat layer made of a curable resin containing the compound (Z) is added to a glass support or a base resin support as the substrate. When using a substrate having a laminated resin layer, it is preferably 0.1 to 5.0 parts by mass, more preferably 0 .2 to 4.0 parts by weight, particularly preferably 0.3 to 3.0 parts by weight. When the content of the compound (Z) is within the above range, good near-infrared absorption properties can be achieved.

<Compound (S)>
In addition to the compound (Z), the substrate may contain a compound (S) having an absorption maximum in a wavelength range of 350 nm or more and less than 700 nm, and the transparent resin substrate contains the compound (S). is preferred.

The compound (S) is not particularly limited as long as it has an absorption maximum at a wavelength of 350 nm or more and less than 700 nm, but it is preferably a solvent-soluble dye compound. Examples of the compound (S) include squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, tetraazaporphyrin-based compounds, porphyrin-based compounds, triarylmethane-based compounds, subphthalocyanine-based compounds, perylene-based compounds, and semi-squarylium-based compounds. , styryl compounds, phenazine compounds, pyridomethene-boron complex compounds, pyrazine-boron complex compounds, pyridone azo compounds, xanthene compounds, and BODIPY (boron dipyrromethene) compounds. Among these, squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, triarylmethane-based compounds, xanthene-based compounds, and pyridone-azo-based compounds are particularly preferred. Compound (S) may be used alone or in combination of two or more.

By containing the compound (S) in the base material, light rays can be cut in the wavelength region where the dielectric multilayer film normally cuts light rays by absorption of the compound (S), so that the number of layers of the dielectric multilayer film can be reduced. Sometimes. In addition, the base material can contain a plurality of types of compound (S). In this case, the absorption maximum wavelength of the compound (S) contained in a plurality of types is preferably 30 nm or more, more preferably 40 nm or more, and particularly preferably They are preferably different from each other by 50 nm or more.

<Other ingredients>
The base material further contains additives such as infrared absorbing dyes, near-ultraviolet absorbents, antioxidants, releasing agents, fluorescence quenching agents, metal complex compounds, etc. may contain. The other components may be used singly or in combination of two or more.

The infrared absorbing dye is preferably a solvent-soluble compound. Examples of infrared absorbing dyes include squarylium-based compounds, phthalocyanine-based compounds, cyanine-based compounds, naphthalocyanine-based compounds, pyrrolopyrrole-based compounds, croconium-based compounds, hexaphylline-based compounds, metal dithiolate-based compounds, perylene-based compounds, and ytterbium complexes. and ring-extended dipyrromethene-based compounds. Among these, squarylium-based compounds are particularly preferred. The infrared absorbing dyes may be used alone or in combination of two or more.

The maximum absorption wavelength of the infrared absorbing dye is preferably 950 nm to 1400 nm, more preferably 960 nm to 1350 nm, even more preferably 965 nm to 1200 nm, particularly preferably 965 nm to 1180 nm. The use of such an infrared-absorbing dye tends to cut off light rays on the longer wavelength side than λ ^θ B ₅₀ more efficiently.

Examples of near-ultraviolet absorbers include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.
Antioxidants include, for example, 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, tris(2,6-di-t-butylphenyl)phosphite and the like.

These additives may be mixed with the resin or the like when manufacturing the base material, or may be added when synthesizing the resin. Further, the amount to be added is appropriately selected according to the desired properties, but it is usually 0.01 to 5.0 parts by mass, preferably 0.05 to 2.0 parts by mass, relative to 100 parts by mass of the resin. is.

<Method for manufacturing base material>
When the base material is a base material containing a transparent resin substrate, the transparent resin substrate can be formed by, for example, melt molding or cast molding. By coating with a coating agent such as a hard coat agent and an antistatic agent, a substrate having an overcoat layer laminated thereon can be produced.

When the substrate is a glass support or a base resin support having a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (Z) laminated thereon, for example, can be obtained by melt-molding or cast-molding a resin solution containing the compound (Z) on a glass support or a base resin support. Alternatively, a glass support or a base resin support is coated with a resin solution containing the compound (Z) by a method such as spin coating, slit coating, or inkjet, and then the solvent is removed by drying. It can be obtained by light irradiation or heating.

≪Melt molding≫
Specifically, melt-molding includes a method of melt-molding pellets obtained by melt-kneading a resin and a compound (Z), and a method of melt-molding a resin composition containing a resin and a compound (Z). method, or a method of melt-molding pellets obtained by removing the solvent from a resin composition containing the compound (Z), resin and solvent. Examples of melt molding methods include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
Cast molding includes a method of casting a resin composition containing the compound (Z), a resin and a solvent on a suitable support and removing the solvent, or a method of removing the solvent from the compound (Z), a photocurable resin and a thermosetting resin. A method of casting a curable composition containing at least one curable resin selected from curable resins on a suitable support, removing the solvent, and then curing by an appropriate technique such as ultraviolet irradiation or heating. is mentioned.

When the substrate is a substrate made of a transparent resin containing the compound (Z), the substrate can be obtained by peeling off the coating film from the molding support after cast molding. In addition, a transparent resin layer such as an overcoat layer made of a curable resin or the like containing the compound (Z) is formed on a support such as a glass support or a base resin support. In the case of a laminated base material, the base material can be obtained by cast molding without peeling off the coating film.

[Dielectric multilayer film]
Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately laminated. A material having a refractive index of 1.8 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index of 1.8 to 4.4 is usually selected. Examples of such materials include diamond, iron oxide, copper oxide, barium titanate, barium sulfide, strontium titanate, cadmium telluride, strontium sulfide, mercury sulfide, cesium oxide, hafnium oxide, titanium oxide, zirconium oxide, Main components are tantalum pentoxide, niobium oxide, antimony oxide, lanthanum oxide, yttrium oxide, zinc oxide, chromium oxide, indium oxide, antimony oxide, zinc sulfide, indium oxide, etc., and small amounts of titanium oxide, tin oxide, cerium oxide, etc. (For example, 0 to 10% by mass with respect to the main component), and those in which material particles having a refractive index of 1.8 or more are dispersed in a transparent resin. Barium titanate, cadmium telluride, cesium oxide, hafnium oxide, titanium oxide, zirconium oxide, tantalum pentoxide, niobium oxide, antimony oxide, oxide Lanthanum and yttrium oxide are preferred. Titanium oxide is preferred from the viewpoint of little change in optical properties when temperature changes.

A material having a refractive index of less than 1.8 can be used as the material constituting the low refractive index material layer, and a material having a refractive index of 1.2 to less than 1.8 is usually selected. Examples of such materials include transparent resin, silicon dioxide (silica), alumina, lanthanum fluoride, barium fluoride, cesium fluoride, aluminum fluoride, lithium fluoride, magnesium fluoride and sodium aluminum hexafluoride ( cryolite) and yttrium fluoride. Among these, silica is preferable from the viewpoint of manufacturing cost, film adhesion and durability, silica having a refractive index of 1.468 or more is more preferable from the viewpoint of changes in optical properties when temperature changes, and silica having a refractive index of 1.47 or more. is more preferred.

The dielectric multilayer film in the optical filter of the present invention preferably comprises a layer made of titanium oxide (TiO ₂ ) and a layer made of silica (SiO ₂ ). Further, it is particularly preferable that all the layers made of SiO ₂ constituting the dielectric multilayer film have a refractive index of 1.47 or more.

A semiconductor layer or conductor layer having a refractive index of 0.1 to 4.5 may be included in the dielectric multilayer film. Such materials include graphite, tungsten, germanium, silicon, silicon monoxide, iron, manganese, platinum, gold, silver, copper, magnesium, tungsten, nickel and aluminum. Such a material makes it possible to increase the difference in refractive index between the high refractive index material layer and the low refractive index material layer. It becomes easy to shield light.

The optical filter of the present invention is preferably made of a material with a small thermal expansion coefficient from the viewpoint of reducing changes in the optical properties of the optical filter when the temperature changes. That is, the refractive index of all layers constituting the dielectric multilayer film is preferably less than 3.5, more preferably 1.0 or more and less than 3.5. It is more preferable that all the layers in the film have a refractive index of 1.0 or more and less than 3.5.

The method of laminating the high refractive index material layer, the low refractive index material layer, and optionally the semiconductor layer and the conductor layer is not particularly limited as long as a dielectric multilayer film is formed by laminating these material layers. For example, directly on the substrate, CVD method, sputtering method, magnetron sputtering method, ion beam sputtering method, radical assisted sputtering method, vacuum deposition method, ion assisted deposition method, ALD method, plasma ALD method, or ion plating deposition A dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated can be formed by a method or the like. Among them, the CVD method, the magnetron sputtering method, the ion beam sputtering method, the radical assist method, the ion assist method, the ALD method, the plasma ALD method, and the ion plating method are used from the viewpoint of little change in optical properties when the temperature changes. Preferably, ion beam sputtering, ion-assisted vapor deposition, and ion plating vapor deposition are more preferable from the viewpoint of ease of production due to high film formation rate, and can prevent excessive temperature rise to the substrate. From a technique point of view, the ion-assisted vapor deposition method is most preferred.

<Ion-assisted vapor deposition method>
The ion-assisted vapor deposition method is a method of irradiating a substrate with oxygen ions or inert gas ions during film formation of a vapor deposition material in vacuum vapor deposition. By controlling the ion current density of the irradiated ions, it is possible to increase the energy of the molecules during film formation without excessively heating the substrate, and a film with a high film density can be obtained even on a resin substrate. be done. Devices that can perform ion-assisted deposition include the SYRUSpro series manufactured by Buehler Leybold Optics, the OTFC series manufactured by Optorun Co., Ltd., the MIC series manufactured by Shincron Co., Ltd., the EPD series, the VCD series manufactured by ShinMaywa Industries, Ltd., ( Showa Shinku Co., Ltd. Sapio series etc. are mentioned.

<Ion current density>
As an index for adjusting the film quality of the obtained dielectric multilayer film, the unit deposition rate obtained by dividing the ion current density per unit area (μA/cm ² ) by the deposition rate (Å/sec)/the ion current density per area ( μA·sec/Å·cm ² ). Since the ion current density varies depending on the distance between the ion gun, which is the ion source, and the substrate, even if the ion gun voltage, current, acceleration voltage and supply gas flow rate are the same, the ion current density may vary depending on the device. Therefore, the ion gun voltage, current, acceleration voltage and supply gas flow rate are adjusted based on the ion current density. The ion current density is calculated from the amount of current applied to an ion current density meter with −30 V applied to a copper plate having a thickness of 1 mm and an area of 1 cm ² .

When a low refractive index layer such as silica is formed, the ion current density is preferably 4 to 30 μA·sec/Å·cm 2 , more preferably 4 to 30 μA·sec/Å·cm ² , from the viewpoint of obtaining a film quality with little change in optical properties when temperature changes. 6 to 25 μA·sec/Å·cm ² , more preferably 8 to 20 μA·sec/Å·cm ² . From the viewpoint of obtaining a silica layer having a refractive index of 1.47 or more, it is preferable to carry out ion irradiation at the above ion current density at a vapor deposition temperature of 110° C. or more. From the viewpoint of obtaining film quality with little change in optical properties when temperature changes, ions generated from a mixed gas of oxygen gas and argon gas are preferable as the ion source.

When a high refractive index layer such as titanium oxide is formed, the ion current density is preferably 12 to 50 μA·sec/Å·cm 2 , more preferably 12 to 50 μA·sec/Å·cm ² from the viewpoint of obtaining a film quality with little change in optical properties when temperature changes. is 14-40 μA·sec/Å·cm ² . When the substrate has a resin layer, the ion current density is preferably 14 to 35 μA·sec/Å·cm ² from the viewpoint of suppressing deterioration of the resin.

From the viewpoint of suppressing substrate deformation due to temperature rise due to ions, the dielectric material and film formation rate are not particularly limited, and the ion current density per unit area is preferably 60 μA/cm ² or less, more preferably 55 μA. / cm ² or less. Although the minimum value is not particularly limited, it is preferably 0.1 μA/cm ² .

The total number of laminated layers of the high refractive index material layer and the low refractive index material layer, and optionally the semiconductor layer and the conductor layer in the dielectric multilayer film is preferably 16 to 120 layers, more preferably 18 layers, as a whole optical filter. ~110 layers, more preferably 20-100 layers. When the total number of laminated layers constituting the dielectric multilayer film is within the above range, a sufficient manufacturing margin can be ensured, and warpage of the optical filter and cracks in the dielectric multilayer film can be reduced.

At least one of the dielectric multilayer films has one minimum value of transmittance between incident angles of 0 to 30 degrees at a wavelength of (λ ^θ B ₅₀ −5) nm. FIG. 7 shows the incident angle dependence of transmittance at a wavelength of 968 nm, which corresponds to the wavelength (λ ^θ B ₅₀ −5) nm of design (I) in Table 5-1. It can be seen from FIG. 7 that the transmittance has a minimum value of 41% at an incident angle of 18 degrees. Owing to such a minimum value, an optical filter with little change in transmittance between incident angles of 0 to 30 degrees can be obtained. Therefore, as an optical filter that transmits near-infrared rays of a specific wavelength and shields light of unnecessary wavelengths, an optical filter that has a special effect of reducing the amount of noise change caused by sunlight when the incident angle changes is obtained.

FIG. 14 shows the incident angle dependence of transmittance at 1000 nm corresponding to the wavelength (λ ^θ B ₅₀ -5) of design (VIII) in Table 6-1. FIG. 14 shows the incident angle dependence of the transmittance of a conventional optical filter having a dielectric multilayer film. Since the transmittance decreases as the incident angle increases, there is no minimum value. Therefore, as the incident angle increases, λ ^θ B ₅₀ shifts to shorter wavelengths, and as a result, the transmission wavelength of near-infrared rays of a specific wavelength shifts to shorter wavelengths.

The transmittance at the minimum value within the incident angle range of 0 to 30 degrees is preferably 60% or less, more preferably 50% or less, and even more preferably 45% or less. If the transmittance is within the above range, the effect of reducing the shift amount of λ ^θ B ₅₀ tends to be exhibited, which is preferable.

The thickness of each layer of the high refractive index material layer and the low refractive index material layer constituting the dielectric multilayer film, and the semiconductor layer and the conductor layer as necessary, is preferably 1 to 1300 nm, more preferably 2 to 1250 nm, and particularly preferably. is between 5 and 1200 nm. When the thickness of each layer is within this range, it is easy to control when forming the film, and there is a tendency to easily control the shielding and transmission of specific wavelengths due to the relationship between the optical characteristics of reflection and refraction.

The dielectric multilayer film preferably includes at least one layer having a physical thickness of preferably 300 nm or more and 800 nm or less, more preferably 350 nm or more and 800 nm or less, further preferably 400 nm or more and 800 nm or less, and includes at least two layers. is more preferred, with at least three layers being particularly preferred. Furthermore, it is preferable to include at least one layer having a thickness of 801 nm or more and 1200 nm or less. By designing the film thickness of the dielectric multilayer film as described above, a dielectric multilayer film having a minimum transmittance between incident angles of 0 degrees and 30 degrees at a wavelength of (λ ^θ B ₅₀ −5) nm can be obtained. As a result, it is possible to obtain an optical filter that transmits near-infrared rays of a specific wavelength with less dependence on the angle of incidence and shields light of unnecessary wavelengths.

[Other functional films]
The optical filter of the present invention is provided between the base material and the dielectric multilayer film, the surface of the base material opposite to the surface on which the dielectric multilayer film is provided, or the dielectric multilayer film, as long as the effects of the invention are not impaired. An antireflection film and a hard coating are applied to the surface of the film opposite to the surface on which the base material is provided, for the purposes of improving the surface hardness of the base material and dielectric multilayer film, improving chemical resistance, antistatic and scratch removal. A functional film such as a coat film, an antistatic film, an adhesion assisting film, a stress adjusting film, a conductive film, and a light shielding film can be appropriately provided.

The optical filter of the present invention may contain one layer of the functional film described above, or may contain two or more layers. When the optical filter of the present invention contains two or more layers of such functional films, it may contain two or more similar layers or two or more different layers.

The method for laminating such a functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent, and an antistatic agent is applied to a base material or a dielectric multilayer film in the same manner as described above, melt molding or A method of cast molding and the like can be mentioned.

It can also be produced by applying a curable composition containing a coating agent and the like onto a base material or a dielectric multilayer film using a bar coater or the like, and then curing the film by ultraviolet irradiation or the like.

Examples of coating agents include ultraviolet (UV) or electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethane, urethane acrylate, acrylate, and epoxy and epoxy acrylate resins. Curable compositions containing these coating agents include vinyl-based, urethane-based, urethane-acrylate-based, acrylate-based, epoxy-based and epoxy-acrylate-based curable compositions.

Moreover, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

The mixing ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, when the total amount of the curable composition is 100% by mass, and further It is preferably 1 to 5% by mass. When the blending ratio of the polymerization initiator is within the above range, the curable composition has excellent curing properties and handling properties, and functional films such as antireflection films, hard coat films, and antistatic films having desired hardness can be obtained. can.

Furthermore, the curable composition may contain an organic solvent as a solvent, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone and propylene. esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N- Amides such as methylpyrrolidone can be mentioned. These solvents may be used singly or in combination of two or more.

The thickness of the functional membrane is preferably 0.1-20 μm, more preferably 0.5-10 μm, particularly preferably 0.7-5 μm.
In addition, for the purpose of improving the adhesion between the base material and the functional film or the dielectric multilayer film and the adhesion between the functional film and the dielectric multilayer film, the surface of the base material, the functional film or the dielectric multilayer film may be subjected to corona treatment or treatment. Surface treatment such as plasma treatment may be performed.

[Applications of optical filters]
The optical filter of the present invention has excellent light transmission characteristics in the wavelength region used for near-infrared sensing, and is characterized by small changes in optical properties due to incident angle and small changes in optical properties when temperature changes. Therefore, it is useful as an optical filter for optical sensor devices and camera modules. In particular, smartphones, tablet terminals, mobile phones, speakers, smart speakers, wearable devices, automobiles, televisions, game machines, aircraft, unmanned aircraft, air conditioners, robots, robot vacuum cleaners, pet robots, agricultural machinery, fingerprint authentication devices, veins It is useful as an optical sensor for an individual imaging device installed in an authentication device, an iris authentication device, a face authentication device, a blood flow sensor, a medical device, a biometric authentication device, and the like.

<Solid-state imaging device>
A solid-state imaging device according to the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor equipped with a solid-state imaging device such as a CCD or CMOS image sensor. Specifically, it includes digital still cameras, smartphone cameras, mobile phone cameras, wearable device cameras, digital It can be used for applications such as video cameras.

<Camera module>
A camera module according to the present invention comprises the optical filter of the present invention. Here, the camera module is a device that includes an image sensor, a focus adjustment mechanism, a phase detection mechanism, a distance measurement mechanism, or the like, and outputs an image and distance information as electrical signals.

<Sensor module>
FIG. 3 shows a configuration example of a sensor module according to the present invention. The sensor module consists of a light source 102, an optical filter 1 and a sensor 112, as shown in FIG. It may have a lens unit 121 as shown in FIG. 3B and may be used as an imaging device or a camera module. For scanning the light source, a light source scanning unit 131 such as a polygon mirror, MEMS, or phased array may be provided in front of the light source 102 as shown in FIG. 3(c). One or more light sources, sensors, and lens units may be provided per module. It may have an ambient light sensor unit 113 having an ambient light sensor 114 as shown in FIG. 3(e). It is more preferable to have an ambient light sensor unit from the viewpoint of enabling noise offset and enabling a highly sensitive sensor module. Based on the obtained information, a biometrics authentication system may be established via a signal processing device as shown in FIGS. 3(a) to 3(e).

≪Light source≫
As the light source 102, an LED, an organic LED, a laser diode, a Yb laser, a photonic crystal surface emitting laser diode (PCSEL), a vertical cavity surface emitting laser (VCSEL), or the like having an emission maximum wavelength of 800 to 1060 nm may be used. can be done. A PCSEL or a VCSEL is more preferable because of the sharpness of the emission wavelength. PCSELs include, for example, L13395-04 manufactured by Hamamatsu Photonics Co., Ltd. VCSELs include, for example, HV94-0015M3 manufactured by Optwell.

≪Sensor≫
As a member constituting the sensor 112, a photoelectric conversion element such as silicon, black silicon, InGaAs, an organic photoelectric conversion film, a rectenna, a graphene sensor, a metamaterial sensor, or the like, which converts light of a specific wavelength into an electric signal can be used. can. One selected from silicon, black silicon and InGaAs is preferable from the viewpoint of near-infrared sensitivity, and silicon and black silicon are more preferable from the viewpoint of manufacturing cost. Moreover, from the viewpoint of stray light suppression, a polarizing filter may be provided. From the viewpoint of noise reduction, it is preferable to use a color filter or the like to reduce the sensitivity to wavelengths in the visible light region. A near-infrared sensor whose sensitivity to wavelengths in the visible light region is reduced through a color filter includes, for example, the sensor described in JP-A-2017-216678.

≪Black Silicon≫
Black silicon may be used for the sensor module, imaging device, camera module, and sensor unit of the biometric authentication device according to the present invention. Black silicon can be obtained, for example, by irradiating a silicon wafer with a laser under a specific atmosphere to form minute spikes on the silicon surface. When black silicon is used, the light receiving sensitivity in the near-infrared band becomes higher than when a silicon photodiode is used, so it is more preferably used. Examples of commercially available sensors using black silicon include XQE series from SiOnyx.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In addition, "parts" means "parts by mass" unless otherwise specified. In addition, the method for measuring each physical property value and the method for evaluating physical properties are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(a) Using a gel permeation chromatography (GPC) device (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS, weight average molecular weight in terms of standard polystyrene (Mw) and number average molecular weight (Mn) were measured.
(b) Using a Tosoh GPC apparatus (HLC-8220, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nanotechnologies Co., Ltd., the temperature was measured at a rate of temperature increase of 20°C per minute under a nitrogen stream.

<Refractive index>
The refractive index of the dielectric multilayer film was calculated by the following procedure.
Reflectance optical monitor using a glass substrate (manufactured by SCHOTT, D263, thickness 0.3 mm) with a light source of 550 nm. A thick dielectric film was formed. Using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Co., Ltd., the obtained substrate with a dielectric film is measured at an angle of 5° from the vertical direction of the surface of the substrate at a wavelength of 300 nm to 1900 nm. Transmittance and absolute reflectance were measured under an environment of room temperature of 25° C. and humidity of 50%. From the obtained transmittance for each wavelength at 5° incidence and absolute reflectance for each wavelength at 5° incidence, the refractive index at a wavelength of 550 nm was calculated using simulation software Essential Macleod (manufactured by Thin Film Center). The refractive index in the dielectric multilayer film and the refractive index of dielectrics formed on different substrates were assumed to be the same as the refractive indices of dielectrics obtained under the same deposition conditions using the above method.

<Spectral transmittance>
The transmittance in each wavelength region of the optical filter was measured at room temperature using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation after standing for one week in a dark environment with a room temperature of 25°C and a humidity of 60%. Measured under an environment of 25° C. and 50% humidity.

Here, the transmittance when measured from the vertical direction of the optical filter is obtained by measuring the light 6 transmitted vertically through the optical filter 1 as shown in FIG. In the transmittance measured at an angle of 30° with respect to the direction, the light 6 ′ transmitted at an angle of 30° with respect to the vertical direction of the optical filter 1 as shown in FIG. It was measured.

<Noise amount change>
The amount of noise is the transmittance T ₀ (λ) and T ₃₀ (λ) for each wavelength at 0° and 30° incidence with respect to the surface of the optical filter, the intensity of sunlight for each wavelength I (λ), and the It was calculated from the sensitivity IR (λ) for each wavelength of the near-infrared sensor obtained by the following formula.
Noise amount change (%) = ( _N30 - _N0 )/ _N0 x 100
N ₃₀ : The total amount of noise on the sensor pixels due to sunlight with a wavelength of 300 to 1200 nm incident at an angle of 30 degrees from the direction perpendicular to the surface of the optical filter. As shown in the following formulas, the transmittance of the optical filter by wavelength (T ₃₀ (λ)), the intensity of sunlight by wavelength (I(λ)), and the sensitivity by wavelength of near-infrared light through the color filter (IR(λ )) and calculated as the sum of calculated values for each 1 nm.
N ₀ : The total amount of noise to the sensor pixel due to sunlight with a wavelength of 300 to 1200 nm incident from the direction perpendicular to the surface of the optical filter. As shown in the following formulas, the transmittance of the optical filter by wavelength (T ₀ (λ)), the intensity of sunlight by wavelength (I (λ)), and the sensitivity by wavelength of near-infrared light through the color filter (IR (λ )) and calculated as the sum of calculated values for each 1 nm.

太陽光線の波長別強度Ｉ（λ）は、図５に示す通り、波長３５０ｎｍ～１２００ｎｍについて、国立研究開発法人新エネルギー・産業技術総合開発機構が公開している、ある日時の岐阜の照射量データを用い、波長３５０ｎｍ未満の強度を０として用いた。カラーフィルターを介した近赤外線センサーの波長別感度は、特開２０１７－２１６６７８号公報の記載に基づき、図４に示す値を用いた。

As shown in Fig. 5, the intensity I (λ) of sunlight by wavelength is the irradiation amount data in Gifu at a certain date and time published by the New Energy and Industrial Technology Development Organization for wavelengths of 350 nm to 1200 nm. was used, and the intensity below a wavelength of 350 nm was used as zero. Sensitivity by wavelength of the near-infrared sensor via a color filter, based on the description of JP-A-2017-216678, the values shown in FIG. 4 were used.

<Change in optical properties when temperature changes>
The optical filter was allowed to stand at 120° C. for 1 hour in a nitrogen atmosphere in an oxygen-free atmosphere thermostat (IPH-202, manufactured by Espec Co., Ltd.). After that, the sample was taken out, and the spectral transmittance measurement was performed in an atmosphere of 120°C. The absolute value of the difference between the λ ⁰ B ₅₀ measured at 25° C. and the λ ⁰ B ₅₀ measured at 120° C. in the above evaluation of the spectral transmittance is less than 4 nm. The thing was set to "x".

[Synthesis example]
The dye compounds used in the following examples were synthesized by a generally known method. General synthesis methods include, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, JP-A-60-228448, JP-A-1-146846, Japanese Patent Application Laid-Open No. 1-228960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. 63-124054, “Phthalocyanine-Chemistry and Function-” (IPC, 1997), Japanese Patent Application Laid-Open No. 2007-169315, Japanese Patent Application Laid-Open No. 2009 -108267, JP-A-2010-241873, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like.

<Resin Synthesis Example 1>
8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene (hereinafter also referred to as “DNM”) 100 represented by the following formula (X ₁ ) 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were placed in a reaction vessel purged with nitrogen, and the solution was heated to 80°C. Next, 0.2 part of a toluene solution of triethylaluminum (0.6 mol/liter) and 0.2 part of a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/liter) were added as polymerization catalysts to the solution in the reaction vessel. 9 parts were added, and this solution was heated and stirred at 80° C. for 3 hours to carry out ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２，０００、重量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。

An autoclave was charged with 1,000 parts of the ring-opened polymer solution thus obtained, and 0.12 part of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution. Then, under the conditions of a hydrogen gas pressure of 100 kg/cm ² and a reaction temperature of 165° C., a hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the resulting reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a solidified product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165°C.

[Example 1]
Into a container, 100 parts by mass of the resin A obtained in Resin Synthesis Example 1, 0.08 parts by mass of the compound (z-5) described in Table 1 above (absorption maximum wavelength 770 nm in dichloromethane) as the compound (Z) , compound (z-35) (absorption maximum wavelength 882 nm in dichloromethane) 0.06 parts by mass, compound (z-65) represented by the following formula (z-65) (absorption maximum wavelength 738 nm in dichloromethane) 0 .42 parts by mass, the compound represented by the following formula (z-66) (z-66) (absorption maximum wavelength 704 nm in dichloromethane) 0.30 parts by mass and the compound represented by the following formula (z-67) (z -67) (maximum absorption wavelength 844 nm in dichloromethane) 0.48 parts by mass, compound (s-1) represented by the following formula (s-1) as compound (S) (maximum absorption wavelength 429 nm in dichloromethane ) 0.80 parts by mass, the compound represented by the following formula (s-2) (s-2) (absorption maximum wavelength 550 nm in dichloromethane) 0.80 parts by mass, the compound represented by the following formula (s-3) (s-3) 0.60 parts by mass (maximum absorption wavelength 606 nm in dichloromethane) and methylene chloride were added to prepare a solution (A1) having a resin concentration of 20% by mass.

After applying the following curable composition solution (1) on one side of a glass substrate (manufactured by SCHOTT, D263, thickness 0.1 mm) by spin coating, it is heated on a hot plate at 80 ° C. for 2 minutes to volatilize the solvent. It was removed to form a resin layer functioning as an adhesive layer with a transparent resin layer to be described later. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the resin layer was about 8 μm. Next, the solution (A1) was applied onto the resin layer using an applicator under conditions such that the film thickness after drying was 50 μm, and heated on a hot plate at 80° C. for 5 minutes to volatilize and remove the solvent. Then, a transparent resin layer was formed. Next, after exposure from the glass surface side using a conveyor type exposure machine (exposure amount 1 J/cm ² , illuminance 200 mW), baking was performed in an oven at 180° C. for 5 minutes to obtain a substrate.

On each surface of the substrate, using an ion-assisted vacuum deposition apparatus, a starting pressure of 0.0001 Pa, a deposition temperature of 120 ° C., and a mixed gas of oxygen and argon as a supply gas to the ion gun, a physical film thickness of 60 nm or less. The layer is controlled by the integrated film thickness of the crystal oscillator, and the ion current density per unit film formation rate (Å/sec) divided by the ion current density per unit area (μA/cm ² ) is 8 μA per area.・A silica layer (SiO ₂ : refractive index of light at 550 nm: 1.47) while performing ion assist of sec/Å·cm ² and ion current density per unit deposition rate of 20 μA·sec/Å·cm ² per unit area. A dielectric multilayer film was provided in which titanium oxide layers (TiO ₂ : refractive index of light of 550 nm: 2.48) were alternately laminated while performing ion assist. At this time, the design (I) shown in Table 5-1 was provided on the glass substrate side, and the design (II) was provided on the transparent resin layer side to obtain an optical filter with a thickness of 0.159 mm. Glass at a wavelength of 968 nm corresponding to the wavelength (λ ^θ B ₅₀ −5) when only the dielectric multilayer film of design (I) is provided on a glass substrate (manufactured by SCHOTT, D263, thickness 0.1 mm). FIG. 7 shows the transmittance when light is incident from 0° to 60° from the vertical direction of the substrate. It can be seen that design (I) is the design with a minimum of 41% at 18 degrees.

Curable composition solution (1): isocyanuric acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Chemical Co., Ltd.) 30 parts, 1,9-nonanediol diacrylate 20 parts, methacrylic acid 20 parts parts, glycidyl methacrylate 30 parts, 3-glycidoxypropyltrimethoxysilane 5 parts, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Chiba Specialty Chemical Co., Ltd.) 5 parts and San-Aid SI-110 main agent ( Sanshin Kagaku Kogyo Co., Ltd.) was mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 50 wt %, and filtered through a Millipore filter with a pore size of 0.2 μm.

The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter has a low noise change of 3% under a solar light source at 0° and 30° incidence, and the change in optical characteristics when temperature changes is "O", which is useful for near-infrared optical sensors. was suitable for

[Example 2]
With respect to the dielectric multilayer film in Example 1, a 0.16 mm thick film was formed in the same manner as in Example 1, except that the design (I) on the glass substrate side was changed to the design (III) shown in Table 5-2. An optical filter was obtained. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter has a low noise change of 15% under a solar light source between 0° and 30° incidence, and the change in optical characteristics when temperature changes is "O", which is useful for near-infrared optical sensors. was suitable for

[Example 3]
With respect to the dielectric multilayer film in Example 1, a 0.154 mm thick film was formed in the same manner as in Example 1, except that the design (I) on the glass substrate side was changed to the design (IV) shown in Table 5-3. An optical filter was obtained. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter has a low noise change of 7% under a solar light source between 0° and 30° incidence, and the change in optical characteristics when temperature changes is "O", which is useful for near-infrared optical sensors. was suitable for

[Example 4]
Regarding the dielectric multilayer film in Example 1, a 0.154 mm thick film was formed in the same manner as in Example 1, except that the design (I) on the glass substrate side was changed to the design (V) shown in Table 5-4. An optical filter was obtained. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter had a low noise change of 6% under a solar light source between 0° and 30° incidence, and the change in optical characteristics when the temperature changed was "O". was suitable for

[Example 5]
In a container, 100 parts by weight of Resin A obtained in Resin Synthesis Example 1, as compound (Z), compound (z-5) 0.04 parts by weight, compound (z-35) 0.03 parts by weight, compound (z -65) 0.21 parts by mass, compound (z-66) 0.15 parts by mass, compound (z-67) 0.24 parts by mass, compound (s-1) 0.40 parts by mass, compound (s-2) ), 0.30 parts by mass of the compound (s-3), and methylene chloride were added to prepare a solution (A2) having a resin concentration of 20% by mass. The obtained solution (A2) was cast on a smooth glass plate, dried at 20° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100° C. under reduced pressure for 8 hours to obtain a substrate made of a transparent resin substrate having a thickness of 0.1 mm.

On each surface of the substrate, using an ion-assisted vacuum deposition apparatus, a starting pressure of 0.0001 Pa, a deposition temperature of 120 ° C., and a mixed gas of oxygen and argon as a supply gas to the ion gun, a physical film thickness of 60 nm or less. The layer is controlled by the integrated film thickness of the crystal oscillator, and the ion current density per unit area is obtained by dividing the ion current density (μA/cm ² ) per unit area by the film formation rate (Å/sec). A silica layer (SiO ₂ : refractive index of light at 550 nm: 1.47) and an ion current density per unit deposition rate of 20 μA·sec/Å·cm ² were formed while performing ion assist of 8 μA·sec/Å·cm 2 . A dielectric multilayer film was provided in which titanium oxide layers (TiO ₂ : refractive index of light of 550 nm: 2.48) were alternately laminated while performing ion assist of cm ² . At this time, design (VI) shown in Table 5-5 was provided on one surface and design (VII) was provided on the other surface to obtain an optical filter with a thickness of 0.106 mm. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter has a low noise change of 14% under a solar light source at 0° and 30° incidence, and the change in optical characteristics when temperature changes is "O", which is useful for near-infrared optical sensors. was suitable for

[Example 6]
In a container, 100 parts by mass of Resin A obtained in Resin Synthesis Example 1, 0.06 parts by mass of compound (z-35), 0.48 parts by mass of compound (z-67) as compound (Z), and methylene chloride was added to prepare a solution (A3) having a resin concentration of 20% by mass. An optical filter was obtained in the same manner as in Example 1, except that the solution (A1) in Example 1 was changed to the solution (A3). The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 3 and FIG. The resulting optical filter has a low noise change of 14% under a solar light source at 0° and 30° incidence, and the change in optical characteristics when temperature changes is "O", which is useful for near-infrared optical sensors. was suitable for

[Comparative Example 1]
In a container, 100 parts by weight of Resin A obtained in Resin Synthesis Example 1, as compound (Z), compound (z-5) 0.08 parts by weight, compound (z-65) 0.42 parts by weight, compound (z -65) 0.30 parts by mass, compound (s-1) 0.80 parts by mass, compound (s-2) 0.80 parts by mass, compound (s-3) 0.60 parts by mass, and methylene chloride are added. to prepare a solution (A4) having a resin concentration of 20% by mass. A substrate was obtained in the same manner as in Example 1, except that the solution (A1) in Example 1 was changed to the solution (A4).

On each surface of the obtained substrate, using an ion-assisted vacuum deposition apparatus, a starting pressure of 0.0001 Pa, a deposition temperature of 120 ° C., and a mixed gas of oxygen and argon as a supply gas to the ion gun, physical deposition of 60 nm or less The film thickness of ^the layer is controlled by the integrated film thickness of the crystal oscillator. A silica layer (SiO ² : refractive index of light at 550 nm: 1.44) and an ion current density of 10 μA·sec/Å per unit deposition rate/area while performing ion assist at a current density of 3 µA·sec/Å·cm 2 _. A dielectric multilayer film was provided in which titanium oxide layers (TiO ₂ : refractive index of light at 550 nm: 2.35) were alternately laminated while performing cm ² ion assist. At this time, the design (VIII) shown in Table 6-1 was provided on the glass substrate side, and the design (IX) was provided on the transparent resin layer side to obtain an optical filter with a thickness of 0.157 mm. The glass at a wavelength of 1000 nm corresponding to the wavelength (λ ^θ B ₅₀ −5) when only the dielectric multilayer film of design (VIII) is provided on the glass substrate (SCHOTT, D263, thickness 0.1 mm) FIG. 14 shows the transmittance when incident from 0° to 60° from the vertical direction of the substrate. It can be seen that design (VIII) is a conventionally known design and does not have a local minimum between 0° and 30°.

The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. Evaluation results are shown in Table 4 and FIG. The obtained optical filter had a noise amount change of 171% under a sunlight light source between 0° and 30° incidence, and the change in optical characteristics with temperature change was "×", and it was used as a near-infrared optical sensor. was unsuitable for

[Comparative Example 2]
An optical filter was obtained in the same manner as in Comparative Example 1 except that the solution (A4) in Comparative Example 1 was changed to the solution (A1). The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. Evaluation results are shown in Table 4 and FIG. The obtained optical filter had a noise amount change of 27% under a sunlight light source between 0° and 30° incidence, and the change in optical characteristics when temperature changed was "×", and it was used as a near-infrared optical sensor. was unsuitable for

[Comparative Example 3]
Regarding the dielectric multilayer film in Comparative Example 2, design (VIII) on the glass substrate side was changed to design (X) shown in Table 6-2, and design (IX) on the transparent resin layer side was changed to design (XI). An optical filter was obtained in the same manner as in Comparative Example 2 except for the above. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. The evaluation results are shown in Table 4 and FIG. The obtained optical filter had a noise amount change of 37% under a solar light source between 0° and 30° incidence, and the change in optical characteristics when temperature changed was "×", and it was used as a near-infrared optical sensor. was unsuitable for

[Comparative Example 4]
A glass substrate (D263 manufactured by SCHOTT, thickness 0.1 mm) is used with an RF magnetron sputtering apparatus, silicon is used as a vapor deposition source, RF power is 300 W, oxygen / (argon + hydrogen + oxygen) is mixed at a mixing ratio of 20%. A silica layer (SiO ₂ : refractive index of light at 550 nm: 1.46) obtained by forming a film while supplying gas at 20 SCCM and a gas with a mixing ratio of 5% hydrogen/(argon+hydrogen) were supplied at 20 SCCM. A dielectric multilayer film was formed by alternately laminating an amorphous silicon layer (α-Si:H: refractive index of light at 550 nm: 4.1) obtained by forming a film while forming a film. At this time, design (XII) shown in Table 6-3 was provided on one side of the base material, and design (XIII) was provided on the other side of the base material to obtain an optical filter with a thickness of 0.107 mm. The obtained optical filter was evaluated for spectral transmittance, change in amount of noise, and change in optical properties upon temperature change. Evaluation results are shown in Table 4 and FIG. The obtained optical filter had a noise amount change of 65% under a sunlight light source between 0° and 30° incidence, and the change in optical characteristics with temperature change was "×", and it was used as a near-infrared optical sensor. was unsuitable for

DESCRIPTION OF SYMBOLS 1... Optical filter 2, 2'... Base material 3, 3'... Dielectric multilayer film 4, 4'... Functional film or absorption layer 5... Light shielding film 6, 6'... Light 7 Spectrophotometer 101 Light source unit 102 Light source 103 Lens or diffractive optical element 111 Sensor unit 112 Sensor 113 Ambient light sensor unit 114. Ambient light sensor 121 Lens unit 122 Lens or diffractive optical element 131 Light source scanning unit 132 Light source scanning element

Claims (15)

An optical filter having a substrate and a dielectric multilayer film formed on at least one surface of the substrate and transmitting at least part of near-infrared rays,
An optical filter that satisfies the following requirements (A) , (B) and (C) at a wavelength of 300 to 1200 nm:
(A) The maximum transmittance T ^θ _MAX (%) in the wavelength range of 900 to 1060 nm is is 50% or more;
(B) λ ^θ _MAX (nm) is the wavelength at which T ^θ _MAX (%) is obtained in light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. and λ ^θ B ₅₀ (nm) is the shortest wavelength at which the transmittance is 50% in the region longer than λ θ _MAX (nm), | ^{λ 0 B} ₅₀ -λ ³⁰ B ₅₀ | is ;
(C) Average transmittance T in the range of 750 to (λ ^θ _MAX -50) nm for light rays incident at an angle of θ degrees (θ is 0 and 30) from the direction perpendicular to the surface of the optical filter The sum of ^θ _AVG(1) (%) and average transmittance T ^θ _AVG(2) (%) in the range from (λ ^θ _MAX +50) to 1110 nm is 20% or less . The optical filter according to claim 1, which further satisfies the following requirement (D):
(D) Transmittance of 50 in a wavelength region shorter than λ ^θ _MAX (nm) for light rays incident at an angle of θ degrees (θ is 0 or 30) from the direction perpendicular to the surface of the optical filter. % is λ ^θ A ₅₀ (nm), |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |≦10. The optical filter according to claim 2 , which further satisfies the following requirement (E):
(E) |λ ⁰ A ₅₀ −λ ³⁰ A ₅₀ |+|λ ⁰ B ₅₀ −λ ³⁰ B ₅₀ |≦15. The optical filter according to any one of claims 1 to 3 , which further satisfies the following requirement (F):
(F) Average transmittance T ^θ _AVG(3) ( %) is 10% or less. The optical filter according to any one of claims 1 to 4 , wherein said T ^θ _MAX (%) is 70% or more. 6. The optical filter according to any one of claims 1 to 5, wherein all layers constituting said dielectric multilayer film have a refractive index of less than 3.5. The optical filter according to any one of claims 1 to 6, wherein the dielectric multilayer film is composed of a layer made of TiO ₂ and a layer made of SiO ₂ . 8. The optical filter according to claim 7 , wherein all layers made of _SiO2 constituting said dielectric multilayer film have a refractive index of 1.47 or more. 9. The optical filter according to any one of claims 1 to 8 , wherein the dielectric multilayer film includes at least one layer having a physical thickness of 300 nm or more and 800 nm or less. At least one of the dielectric multilayer films has one minimum value of transmittance between an incident angle of 0 degree and 30 degrees at a wavelength of (λ ^θ B ₅₀ -5) nm. 10. The optical filter according to any one of 9 . The optical filter according to any one of claims 1 to 10 , which is for an optical sensor device. An optical sensor device comprising an optical filter according to any one of claims 1-11 . A biometric authentication device comprising the optical filter according to any one of claims 1 to 11 . A solid-state imaging device comprising the optical filter according to any one of claims 1 to 11 . A camera module comprising the optical filter according to any one of claims 1-11 .